JP6285781B2 - Crystallization accelerator - Google Patents

Description

  The present invention relates to an additive (or modifier) for promoting crystallization of a crystalline resin such as an aromatic polyester resin.

  Compounds having a fluorene skeleton (such as a 9,9-bisphenylfluorene skeleton) are known to have excellent functions such as a high refractive index and high heat resistance. As a method for expressing the excellent function of such a fluorene skeleton in a resin and making it moldable, a fluorene compound having a reactive group (hydroxyl group, amino group, etc.), for example, bisphenol fluorene (BPF), biscresol fluorene, etc. In general, a method in which (BCF), bisphenoxyethanol fluorene (BPEF), or the like is used as a constituent component of a resin and a fluorene skeleton is introduced into a part of the skeleton structure of the resin.

  For example, JP-A-2002-284864 (Patent Document 1) discloses a molding material composed of a polyester-based resin having a 9,9-bisphenylfluorene skeleton. JP 2002-284834 A (Patent Document 2) discloses a polyurethane resin having a 9,9-bisphenylfluorene skeleton and crosslinked with a crosslinking agent. In these documents, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (bisphenoxyethanol) are used as part of the diol component constituting the resin. Fluorene skeleton is introduced into the resin.

  However, in such a method, since the resin skeleton is replaced with a fluorene skeleton, a complicated polymerization reaction is required, and the method cannot be applied to a wide range of resins.

  On the other hand, attempts have been made to add a fluorene compound directly to a resin without polymerizing it. For example, Japanese Unexamined Patent Application Publication No. 2005-162785 (Patent Document 3) discloses a resin composition composed of a compound having a 9,9-bisphenylfluorene skeleton and a thermoplastic resin. This document describes that a compound having a 9,9-bisphenylfluorene skeleton can be added to a thermoplastic resin to impart a high refractive index to the thermoplastic resin. In the example, a transparent resin film is prepared by mixing 30 to 40 parts by weight of a specific compound (bisphenol fluorenediglycidyl ether, bisphenoxyethanol fluorene or bisphenoxyethanol fluoredenyl acrylate) with 100 parts by weight of polycarbonate resin. And that the refractive index has increased.

  JP 2011-8017 A (Patent Document 4) discloses an optical resin composition comprising a transparent resin and a fluorene compound having a 9,9-bisarylfluorene skeleton. And this document describes that the birefringence can be reduced without impairing the mechanical properties and heat resistance of the transparent resin, and in a specific example, the fluorene-containing polyester resin is compared with the polycarbonate resin. And 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis (4-glycidyloxyphenyl) fluorene, or 9,9-bis (4-hydroxy-3-methylphenyl) It is described that a stretched film is prepared from a resin composition containing fluorene and birefringence is lowered.

  Furthermore, JP 2011-21083 A (Patent Document 5) discloses that a phenol compound functions as a nucleating agent (β crystal nucleating agent) for forming a β crystal structure in a crystalline resin such as polylactic acid. Have been described. In the examples of this document, 1 to 5% by weight of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is added to the α-crystal (melting point: 168 ° C.) poly-L lactic acid and melted. Kneaded to obtain poly L-lactic acid in which β crystals (melting point: 163 ° C.) were formed, and Tg was changed from 56.5 ° C. to 60.9-62.1 ° C. as the crystal structure was changed. It is described that changed.

JP 2002-284864 A (Claims, Examples) JP 2002-284834 A (Claims, Examples) JP-A-2005-162785 (Claims, Examples) Examples) JP2011-8017 A (Claims, Examples) JP 2011-21083 A (Claims, Examples)

  An object of the present invention is to provide an additive (or modifier) that can promote (or improve or improve) crystallization (or crystallinity) of a crystalline resin.

  Another object of the present invention is an additive capable of promoting crystallization while improving rather than impairing various characteristics (for example, mechanical characteristics, heat resistance, optical characteristics such as Abbe number) of the crystalline resin. Is to provide.

  As described above, although several techniques for adding a compound having a fluorene skeleton to a resin have been reported, the addition of a specific resin improves the refractive index, reduces birefringence, and reduces the crystal structure. The change from the α crystal to the β crystal has been observed, and the present situation is that the development has not been made yet.

  Under such circumstances, the present inventors have intensively studied to solve the above problems, and as a result, among the resins, particularly when a compound having a 9,9-bisarylfluorene skeleton is added to the crystalline resin, Surprisingly, not only is the decrease in crystallinity (plasticizer function) that is a common phenomenon when using low molecular weight compounds as additives, but rather the crystallization of the crystalline resin is promoted. (Or functions as an antiplasticizer for a crystalline resin), and with the promotion of such crystallization, various resin properties are not impaired, but rather can be further improved or improved depending on the resin properties. As a result, the present invention was completed.

  That is, the additive of the present invention is an additive for accelerating crystallization of a crystalline resin (crystalline thermoplastic resin), and is composed of a compound having a 9,9-bisarylfluorene skeleton. Accelerator (crystal nucleating agent, crystallization improver). For example, in the crystalline resin, the additive of the present invention is used to increase (or improve) the heat of fusion, decrease the crystallization start temperature (Tc) when the temperature rises, and increase the crystallization start temperature (Tc) when the temperature decreases ( Or at least one selected from crystallization half-time reduction (or reduction) in isothermal crystallization.

  The compound having a 9,9-bisarylfluorene skeleton may be, for example, a compound represented by the following formula (1).

[Wherein ring Z is an aromatic hydrocarbon ring, R ¹ and R ² are substituents, X is a group — [(OR ³ ) nY] (wherein Y is a hydroxyl group, a mercapto group, glycidyl An oxy group or a (meth) acryloyloxy group, R ³ is an alkylene group, n is an integer of 0 or more) or an amino group, k is an integer of 0 to 4, m is an integer of 0 or more, and p is 1 or more. Indicates an integer. ]
In particular, the compound having a 9,9-bisarylfluorene skeleton may be a compound represented by the following formula (1A).

(In the formula, Z, R ¹ , R ² , k, m, R ³ , n, and p are the same as those in the formula (1).)
In the above formula (1) or (1A), the ring Z may be a monocyclic or condensed polycyclic aromatic hydrocarbon ring (for example, a benzene ring, a naphthalene ring, etc.), and R ¹ is an alkyl group. K may be 0 or 1, and R ² is an alkyl group (eg, a C _1-4 alkyl group), a cycloalkyl group, an aryl group (eg, a C _6-10 aryl group). , An aralkyl group or an alkoxy group, m may be 0 to 2, R ³ may be a C _2-4 alkylene group (for example, a C _2-3 alkylene group), and n is It may be 0 to 2 (for example, 1 or 2), and p may be 1 to 3 (for example, 1 or 2).

  The compounds having a 9,9-bisarylfluorene skeleton typically include 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene, 9,9-bis (aryl- Hydroxyphenyl) fluorene, 9,9-bis (di or trihydroxyphenyl) fluorene, 9,9-bis (hydroxynaphthyl) fluorene, 9,9-bis (hydroxyalkoxyphenyl) fluorene, 9,9-bis (alkyl-) It may be at least one selected from hydroxyalkoxyphenyl) fluorene, 9,9-bis (aryl-hydroxyalkoxyphenyl) fluorene, and 9,9-bis (hydroxyalkoxynaphthyl) fluorene.

  In particular, the effect of promoting crystallization is that the compound having a 9,9-bisarylfluorene skeleton has 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes (n is 1 or more in the above formula (1A)). In the case of a compound), there are many cases where it can be remarkably confirmed. Therefore, a compound having a 9,9-bisarylfluorene skeleton includes, for example, 9,9-bis (hydroxyalkoxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyalkoxyphenyl) fluorene, and 9,9-bis (aryl). It may be at least one selected from -hydroxyalkoxyphenyl) fluorene and 9,9-bis (hydroxyalkoxynaphthyl) fluorene.

  The crystalline resin may contain, for example, an aromatic polyester resin (for example, a polyalkylene arylate resin such as a polyalkylene naphthalate resin). In addition, the additive of the present invention often exhibits a remarkable crystallization promoting effect in such a crystalline resin. Therefore, in particular, compounds having a 9,9-bisarylfluorene skeleton include 9,9-bis (hydroxyalkoxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyalkoxyphenyl) fluorene, and 9,9-bis (aryl). It may be at least one selected from -hydroxyalkoxyphenyl) fluorene and 9,9-bis (hydroxyalkoxynaphthyl) fluorene, and the crystalline resin may be an aromatic polyester resin.

  The additive of the present invention can improve or improve not only the crystallization promoting effect but also various properties. For example, the additive of the present invention further includes (1) mechanical strength [for example, tensile strength, bending strength, and storage elastic modulus E ′ (for example, storage elastic modulus E at room temperature or normal temperature (about 15 to 30 ° C.)). It may be an additive for improving at least one selected from '). The additive of the present invention may further be (2) an additive for improving (or increasing) the Abbe number (particularly the Abbe number and refractive index). Further, the additive of the present invention further includes (3) heat resistance [for example, glass transition temperature (for example, glass transition temperature by DSC (differential scanning calorimetry), glass transition temperature by DMA (dynamic viscoelasticity measurement), etc.) ) Etc.] may be improved (or improved or increased). That is, it is useful as an additive for improving (1) mechanical strength, (2) Abbe number, and / or (3) heat resistance.

  The present invention also includes a resin composition containing a crystalline resin and the crystallization accelerator. In such a resin composition, the crystalline resin may be an aromatic polyester resin such as a polyalkylene naphthalate resin, and the compound having a 9,9-bisarylfluorene skeleton constituting the crystallization accelerator is 9,9-bis (hydroxyalkoxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyalkoxyphenyl) fluorene, 9,9-bis (aryl-hydroxyalkoxyphenyl) fluorene, and 9,9-bis (hydroxyalkoxynaphthyl) It may be at least one selected from fluorene.

  In such a resin composition, the proportion of the crystallization accelerator may be about 0.1 to 50 parts by weight with respect to 100 parts by weight of the crystalline resin.

  Moreover, the molded object formed with the said resin composition is also contained in this invention. Such a molded body may be an optical molded body (such as an optical film). Further, the molded body of the present invention may be a film (film-shaped molded body), and such a molded body may be a stretched film.

  The present invention also includes a method of promoting the crystallization of the crystalline resin by adding the crystallization accelerator to the crystalline resin. Furthermore, a method for improving at least one characteristic selected from (1) mechanical strength, (2) Abbe number, and (3) heat resistance is also included.

  In the present specification, “9,9-bis (hydroxyaryl) fluorenes” and “9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes” mean “9,9-bis (hydroxyaryl)”. As long as it has “) fluorene skeleton” or “9,9-bis (hydroxy (poly) alkoxyaryl) fluorene skeleton”, it includes compounds having substituents on aryl groups and fluorene skeletons (specifically, positions 2 to 7 of fluorene) Use for meaning. Furthermore, in this specification, “9,9-bis (hydroxy (poly) alkoxyaryl) fluorene” means 9,9-bis (hydroxyalkoxyaryl) fluorene and 9,9-bis (hydroxypolyalkoxyaryl) fluorene. Used to mean including

  The additive of the present invention can promote (or improve or improve) crystallization (or crystallinity) of a crystalline resin such as an aromatic polyester resin. Although such an additive is a low-molecular compound that is not resinous (that is, a compound having a 9,9-bisarylfluorene skeleton), it does not impair various resin properties, and thus has very usefulness. high. In particular, the additive of the present invention can further improve (or improve) or modify the resin properties depending on the resin properties. For example, the additive of the present invention unexpectedly improves mechanical strength and heat resistance, and increases the Abbe number while increasing the refractive index. In addition, the heat resistance with the mechanical strength and the glass transition temperature (Tg) as an index is usually decreased by the addition of a low molecular compound, and generally the Abbe number decreases as the refractive index increases. These are also surprising effects. Furthermore, according to the additive of the present invention, birefringence (for example, orientation birefringence) of a crystalline resin such as an aromatic polyester resin can be reduced. Therefore, the additive of the present invention not only promotes crystallization but also improves or modifies other resin properties [for example, mechanical properties, thermal properties (heat resistance, etc.) and optical properties]. (Or a modifier) can also be used.

  The additive of the present invention is an additive (crystallization accelerator, crystallinity improver, crystal nucleating agent) for promoting (or improving) crystallization (or crystallinity) of a crystalline resin. The additive is composed of a compound having a 9,9-bisarylfluorene skeleton (hereinafter sometimes referred to as a fluorene compound).

[Fluorene compound]
The fluorene compound only needs to have a 9,9-bisarylfluorene skeleton, and has no reactive group [for example, 9,9-bisarylfluorene (for example, 9,9-bisphenylfluorene). A compound in which p is 0 in formula (1) described later] may be used, but usually has a reactive group.

  Examples of the reactive group include a hydroxyl group, mercapto group, carboxyl group, amino group, (meth) acryloyloxy group, epoxy group (for example, glycidyloxy group) and the like. The fluorene compound may have these reactive groups singly or in combination of two or more.

  The reactive group may be directly bonded to 9,9-bisarylfluorene, or may be bonded via an appropriate linking group (for example, a (poly) oxyalkylene group).

  Specific examples of the fluorene compound include a compound represented by the following formula (1).

[Wherein ring Z is an aromatic hydrocarbon ring, R ¹ and R ² are substituents, X is a group — [(OR ³ ) nY] (wherein Y is a hydroxyl group, a mercapto group, glycidyl An oxy group or a (meth) acryloyloxy group, R ³ is an alkylene group, n is an integer of 0 or more) or an amino group, k is an integer of 0 to 4, m is an integer of 0 or more, and p is 1 or more. Indicates an integer. ]

In the above formula (1), examples of the aromatic hydrocarbon ring represented by the ring Z include a monocyclic aromatic hydrocarbon ring (such as a benzene ring), a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic ring Hydrocarbons (eg, C _8-20 condensed bicyclic hydrocarbons such as indene and naphthalene, preferably C _10-16 condensed bicyclic hydrocarbons), condensed tricyclic hydrocarbons (eg, anthracene, phenanthrene, etc.) Condensed bi- to tetracyclic hydrocarbons, etc.], and ring-assembled hydrocarbon rings (bi- or ter C _6-10 arene rings such as biphenyl ring, terphenyl ring, binaphthyl ring). The two rings Z may be the same or different rings, and may usually be the same ring. Preferred rings Z include a benzene ring, a naphthalene ring, and a biphenyl ring, and may be a benzene ring.

In the formula (1), examples of the group R ¹ include a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydrocarbon group [eg, an alkyl group, an aryl group (C ₆ such as a phenyl group). _-10 aryl group) and the like] and acyl groups (for example, alkylcarbonyl groups such as methylcarbonyl, ethylcarbonyl, pentylcarbonyl, etc.) and the like, and in particular, alkyl groups are often used. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, such as _{C 1-12} alkyl group _{(e.g., C 1-8} alkyl groups, especially methyl groups, such as t- butyl group _{C 1- 4} alkyl group) and the like. In addition, when k is plural (2 to 4), the types of the plural groups R ¹ may be the same or different from each other. The types of the groups R ¹ substituted on different benzene rings may be the same or different from each other. Further, the bonding position (substitution position) of the group R ¹ is not particularly limited, and examples thereof include the 2nd, 7th, 2nd and 7th positions of the fluorene ring. The preferred substitution number k is 0 to 1, in particular 0. The two substitution numbers k may be the same or different.

The substituent R ² substituted on the ring Z is usually a non-reactive substituent, for example, an alkyl group (eg, a C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, C _1-8 alkyl group etc.), cycloalkyl group (C _5-8 cycloalkyl group such as cyclohexyl group), aryl group (eg, phenyl group, tolyl group, xylyl group, naphthyl group etc.) _6-10 an aryl group), a hydrocarbon group such as an aralkyl group (a benzyl group and _{C 6-10} aryl _{-C 1-4} alkyl group such as a phenethyl group); an alkoxy group (methoxy group, _{C 1} such as ethoxy groups _-8 an alkoxy group), such as C _5-10 cycloalkyl group such as a cycloalkoxy group (hexyloxy group cyclohexylene), an aryloxy group (Fe _{C 6-10} aryloxy groups such as alkoxy groups), the radical -OR [expression such aralkyloxy groups _{(C 6-10} aryl _{-C 1-4} alkyl group such as a benzyl group), R is a hydrocarbon radical (Such as the hydrocarbon groups exemplified above). A group such as an alkylthio group (such as a C _1-8 alkylthio group such as a methylthio group) —SR (wherein R is as defined above); an acyl group (such as a C _1-6 acyl group such as an acetyl group); Alkoxycarbonyl group (C _1-4 alkoxy-carbonyl group such as methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom etc.); nitro group; cyano group; substituted amino group (for example, dimethyl) And a dialkylamino group such as an amino group).

Preferred group R ² includes a hydrocarbon group [eg, alkyl group (eg, C _1-6 alkyl group), cycloalkyl group (eg, C _5-8 cycloalkyl group), aryl group (eg, C _6-10 Aryl group), aralkyl group (for example, C _6-8 aryl-C _1-2 alkyl group and the like), alkoxy group (C _1-4 alkoxy group and the like) and the like. Further preferred groups R ² include an alkyl group [C _1-4 alkyl group (particularly methyl group) and the like], an aryl group [eg C _6-10 aryl group (particularly phenyl group) and the like] and the like. Incidentally, when the group R ² is an aryl group, a group R ^2, together with the ring Z, it may form the ring assembly hydrocarbon ring.

In the same ring Z, when m is plural (two or more), the types of the groups R ² may be the same or different from each other. In the two rings Z, the type of the group R ² may be the same or different. The number of substitutions m can be selected according to the type of ring Z, and may be, for example, 0 to 8, preferably 0 to 4 (for example, 0 to 3), and more preferably 0 to 2. In different rings Z, the number of substitutions m may be the same or different from each other.

In the group X of the formula (1), examples of the alkylene group represented by the group R ³ include C _2-6 alkylene such as ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, and tetramethylene group. Group, preferably a _C2-4 alkylene group, more preferably a _C2-3 alkylene group. When n is 2 or more, the type of alkylene group may be composed of different alkylene groups, and may be generally composed of the same alkylene group. In the two aromatic hydrocarbon rings Z, the type of the group R ³ may be the same or different.

The number (additional number of moles) n of the oxyalkylene groups (OR ³⁾ may be any of 0 or more (e.g., 0-20), for example, 0 to 15 (e.g., 1-12), preferably 0-10 ( For example, it may be 1 to 6), more preferably 0 to 4 (for example, 1 to 4), particularly 0 to 2 (for example, 1 or 2). Further, depending on the type of resin, there may be a case where a remarkable improvement effect is obtained when n is 0 or when n is 1 or more. Therefore, either a compound in which n is 0 or a compound in which n is 1 or more may be selected depending on the type of resin. The number of substitutions n may be the same or different for different rings Z.

Preferred X is a group-[(OR ³ ) nY], and particularly Y is preferably a hydroxyl group. In addition, in Formula (1), the compound whose Y is a hydroxyl group is represented by following formula (1A).

(In the formula, Z, R ¹ , R ² , k, m, R ³ , n, and p are the same as those in the formula (1).)
The substitution number p of the group X may be 1 or more (for example, 1 to 6), and may be, for example, 1 to 4, preferably 1 to 3, more preferably 1 to 2, particularly 1. In addition, the substitution number p may be the same or different in each ring Z, and is usually the same in many cases.

  In the formula (1) [or (1A)], the substitution position of the group X is not particularly limited as long as it is substituted at an appropriate substitution position of the ring Z. For example, when the ring Z is a benzene ring, the group X may be substituted at the 2- to 6-position of the phenyl group, and preferably at the 4-position. In addition, when the ring Z is a condensed polycyclic hydrocarbon ring, the group X is a hydrocarbon ring different from the hydrocarbon ring bonded to the 9-position of fluorene in the condensed polycyclic hydrocarbon ring (for example, naphthalene In many cases, the ring is substituted at least on the 5th and 6th positions of the ring.

Specific fluorene compounds (or the compounds represented by the formula (1) or (1A)) include 9,9-bis (hydroxyaryl) fluorenes [or 9,9-bis (hydroxyaryl) fluorene skeletons. Compounds having, for example, 9,9-bis (hydroxyphenyl) fluorenes, 9,9-bis (hydroxynaphthyl) fluorenes], 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes [or 9,9 -Compounds having a bis (hydroxy (poly) alkoxyaryl) fluorene skeleton, such as 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes, 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorenes] X is a group in the formula (1), such as ^{- [(OR 3) n-} OH] , compound; this In al compounds, hydroxyl group, mercapto group, and the like glycidyloxy group or a (meth) acrylate compound substituted acryloyloxy group.

The 9,9-bis (hydroxyphenyl) fluorenes include, for example, 9,9-bis (hydroxyphenyl) fluorene [for example, 9,9-bis (4-hydroxyphenyl) fluorene], 9,9-bis (alkyl -Hydroxyphenyl) fluorene [e.g., 9,9-bis such as 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene (Mono- or di-C _1-4 alkyl-hydroxyphenyl) fluorene], 9,9-bis (aryl-hydroxyphenyl) fluorene [eg, 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene, etc. , 9-bis (mono- or _{di-C 6-10} aryl - hydroxyphenyl) fluorene], 9,9-bis ( Rehydroxyphenyl) fluorene [for example, 9,9-bis (di- or trihydroxyphenyl) such as 9,9-bis (3,4-dihydroxyphenyl) fluorene, 9,9-bis (2,4-dihydroxyphenyl) fluorene ) Fluorene].

  In addition, as 9,9-bis (hydroxynaphthyl) fluorenes, compounds corresponding to the 9,9-bis (hydroxyphenyl) fluorenes in which a phenyl group is substituted with a naphthyl group, for example, 9,9-bis ( Hydroxynaphthyl) fluorene [eg, 9,9-bis (6-hydroxy-2-naphthyl) fluorene, 9,9-bis (5-hydroxy-1-naphthyl) fluorene] and the like.

9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes include, for example, 9,9-bis (hydroxyalkoxyphenyl) fluorene {eg, 9,9-bis [4- (2-hydroxyethoxy) phenyl] 9,9-bis (hydroxyC _2-4 alkoxyphenyl) fluorene} such as fluorene, 9,9-bis [4- (2-hydroxypropoxy) phenyl] fluorene}, 9,9-bis (alkyl-hydroxyalkoxyphenyl) Fluorene {eg, 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-methylphenyl] fluorene, 9, Such as 9-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene 9,9-bis (mono or di C _1-4 alkyl-hydroxy C _2-4 alkoxyphenyl) fluorene}, 9,9-bis (aryl-hydroxyalkoxyphenyl) fluorene {eg, 9,9-bis [4- 9,9-bis (mono or di C _6-10 ) such as (2-hydroxyethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-phenylphenyl] fluorene 9,9-bis (hydroxyalkoxyphenyl) fluorenes such as aryl- _{hydroxyC 2-4} alkoxyphenyl) fluorene} (a compound in which n is 1 in the formula (1)); 9,9-bis (hydroxydi) Alkoxyphenyl) fluorene {eg, 9,9-bis {4- [2- (2-hydroxyethoxy) ethoxy] phenyl Eniru} 9,9-bis (hydroxy polyalkoxy phenyl) fluorene such as 9,9-bis fluorene _{(hydroxy-di-C 2-4} alkoxyphenyl) fluorene} (In Formula (1), with n is 2 or more A certain compound) and the like.

Further, as 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorenes, compounds corresponding to the 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes, wherein a phenyl group is substituted with a naphthyl group, For example, 9,9-bis (hydroxyalkoxynaphthyl) fluorene {eg, 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene, 9,9-bis [6- (2-hydroxypropoxy) ), and the like-2-naphthyl] fluorene such as 9,9-bis (hydroxy _{C 2-4} alkoxy naphthyl) fluorene} etc. 9,9-bis (hydroxyalkoxy naphthyl) fluorenes.

Among these fluorene compounds, in particular, 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene [for example, 9,9-bis (mono or diC _1-4 alkyl- Hydroxyphenyl) fluorene], 9,9-bis (aryl-hydroxyphenyl) fluorene [e.g., 9,9-bis (mono or di _C6-10 aryl-hydroxyphenyl) fluorene], 9,9-bis (di or A compound in which n is 0 in the formula (1A) such as trihydroxyphenyl) fluorene and 9,9-bis (hydroxynaphthyl) fluorene; 9,9-bis (hydroxyalkoxyphenyl) fluorene {for example, 9,9-bis (hydroxy _{C 2-4} alkoxyphenyl) fluorene}, 9,9-bis (alkyl - hydroxy alkoxyphenyl) fluorene {e.g., 9,9-bis (mono- or _{di-C 1-4} alkyl - hydroxy _{C 2-4} alkoxyphenyl) fluorene}, 9,9-bis (aryl - hydroxyalkoxy phenyl) fluorene {e.g. 9,9-bis (mono or di C _6-10 aryl-hydroxy C _2-4 alkoxyphenyl) fluorene}, 9,9-bis (hydroxyalkoxynaphthyl) fluorene {eg, 9,9-bis (hydroxy C _{2 In the} formula (1A) such as -4alkoxynaphthyl) fluorene}, a compound in which n is 1 or more (for example, 1 to 4, preferably 1 to 2, more preferably 1) is preferable.

  Fluorene compounds may be used alone or in combination of two or more. The fluorene compound may be a commercially available product or may be synthesized by a conventional method.

[Crystalling Accelerator and Resin Composition]
As described above, the additive (fluorene compound) of the present invention is used as an additive (crystallization accelerator, crystallization improver, crystal nucleator) for promoting (or increasing or improving) crystallization of a crystalline resin. Can be used. That is, the crystallinity of the resin composition containing the fluorene compound is increased by adding or mixing the fluorene compound to the crystalline resin.

  In the present invention, the effect of promoting (or improving) crystallization is not particularly limited. For example, increase (or improvement) in heat of fusion, decrease in crystallization start temperature (Tc) during temperature increase, temperature decrease. This can be confirmed by an increase (or improvement) in crystallization start temperature (Tc) at the time, a decrease (or reduction) in crystallization half time in isothermal crystallization, and the like.

  It should be noted that the promotion of crystallization of the additive of the present invention usually does not involve a change in crystal form as in Patent Document 5. That is, the additive of the present invention may be an additive for promoting crystallization without changing the crystal form of the crystalline resin.

  Examples of crystalline resins (crystalline thermoplastic resins) include polyolefin resins (ethylene resins such as polyethylene, propylene resins such as polypropylene, ethylene-propylene copolymers, etc.), vinyl alcohol resins (ethylene-vinyl). Alcohol copolymers), aromatic polyester resins, polyamide resins (polyamides 6, 12, 11, 4-6, 6-6, 6-10, 6-12 and other aliphatic polyamides, MXD-6 and other aromatics Polyamide resin, etc.), polyacetal resin (homopolymer or copolymer), polyphenylene sulfide resin, polyether ether ketone resin, polyether nitrile resin, aliphatic polyketone resin (copolymer of ethylene and / or propylene and carbon monoxide), etc. Can be illustrated. These crystalline resins can be used alone or in combination of two or more. Preferred crystalline resins are highly versatile thermoplastic resins such as polyolefin resins, aromatic polyester resins, and polyamide resins. Further, from the viewpoint of mechanical properties and optical properties, a preferred crystalline resin is an aromatic polyester resin.

  Examples of aromatic polyester resins include polyalkylene arylate resins, polyarylate resins [for example, aromatic dicarboxylic acids (such as terephthalic acid) and aromatic diols (biphenol, bisphenol A, xylylene glycol, alkylene oxide adducts thereof, etc.) And the like)], and liquid crystalline polyester resins.

Examples of the polyalkylene arylate resin include a polyalkylene terephthalate resin [for example, a polyalkylene terephthalate (for example, poly C _2-4 alkylene terephthalate such as polyethylene terephthalate, polypropylene terephthalate), a copolymer having an alkylene terephthalate unit (polyalkylene terephthalate unit). polyester etc.], polyalkylene naphthalate resins [for example, polyalkylene naphthalate (e.g., poly C _2-4 alkylene naphthalate such as polyethylene naphthalate), copolyester having an alkylene naphthalate unit (polyalkylene naphthalate units) such as ], Polycycloalkane dialkylene terephthalate resin [for example, polycycloalkane dialkylene terephthalate (for example, , Poly cyclohexane dimethylene terephthalate), such as a copolyester having cycloalkandienyl alkylene terephthalate units (poly cycloalkane alkylene terephthalate unit), and the like.

In the copolyester, examples of the copolymer component include a diol component [eg, alkane diol (eg, C _2-6 alkane diol such as ethylene glycol, propylene glycol, butane diol, hexane diol), polyalkane diol (eg, diethylene glycol). Di-hexaC _2-4 alkanediols such as polytetramethylene glycol), alicyclic diols (eg 1,4-cyclohexanedimethanol etc.), aromatic diols (eg C _2-4 alkylenes of bisphenols) Oxide adducts etc.)], dicarboxylic acid components {eg, aliphatic dicarboxylic acids (eg, C _4-12 alkane dicarboxylic acids such as glutaric acid, adipic acid, sebacic acid), aromatic dicarboxylic acids [eg, asymmetric aromatics] Zika Rubonic acid (eg phthalic acid, isophthalic acid etc.), diphenyldicarboxylic acid etc.]}, hydroxycarboxylic acid component (eg hydroxybenzoic acid etc.) and the like. The copolymerization components may be used alone or in combination of two or more.

  In the copolyester, the proportion of alkylene arylate units (alkylene terephthalate units, alkylene naphthalate units, etc.) may be, for example, 40% by weight or more, preferably 50% by weight or more.

  The aromatic polyester resin may have a linear structure or a branched structure. Aromatic polyester resins may be used alone or in combination of two or more.

  The molecular weight of the crystalline resin (such as aromatic polyester resin) can be selected according to the type of the resin. For example, the number average molecular weight can be selected from a range of 2000 or more (for example, 3000 or more) and 5000 or more (for example, 8000 to 1000000), preferably 10,000 or more (for example, 12000 to 800000), more preferably 15000 or more (for example, 20000 to 500000). The molecular weight can be measured using a conventional method such as gel permeation chromatography (GPC), and may be evaluated as a molecular weight in terms of polystyrene.

  The proportion of the crystallization accelerator (fluorene compound) used is, for example, 0.01 parts by weight or more, for example, 0.1 parts by weight or more (for example, 100 parts by weight of a crystalline resin (aromatic polyester resin etc.)) 0.2 to 200 parts by weight) can be selected, and 0.3 to 100 parts by weight (for example, 0.5 to 80 parts by weight), preferably 1 to 50 parts by weight (for example, 1 to 20 parts by weight). Usually, it can be selected from a range of about 0.01 to 50 parts by weight (for example, 0.05 to 30 parts by weight), for example, 0.1 to 50 parts by weight (for example, 0.5 to 50 parts by weight), preferably 0.2 to 40 parts by weight (for example, 0.5 to 40 parts by weight), more preferably about 0.3 to 30 parts by weight (for example, 0.7 to 30) parts by weight. It may be.

  Since the crystallization accelerator of the present invention can obtain the effect of promoting crystallization efficiently even in a small amount, for example, the use ratio of the crystallization accelerator is set to 100 parts by weight of a crystalline resin (aromatic polyester resin or the like). 20 parts by weight or less (eg 0.1 to 18 parts by weight), preferably 15 parts by weight or less (eg 0.2 to 12 parts by weight), more preferably 10 parts by weight or less (eg 0.3 to 0.3 parts by weight). 7 parts by weight), particularly 5 parts by weight or less (for example, 0.5 to 5 parts by weight).

  In addition, the crystallization accelerator of the present invention is excellent in affinity for a crystalline resin (such as an aromatic polyester resin) and can often maintain or improve the resin characteristics at a high level even when added in a relatively large proportion. The proportion of the crystallization accelerator used is 20 parts by weight or more (for example, 20 to 100 parts by weight), preferably 25 parts by weight or more (for example, for 100 parts by weight of the crystalline resin (aromatic polyester resin or the like)). 25 to 80 parts by weight), more preferably 30 parts by weight or more (for example, 30 to 70 parts by weight).

  Thus, a crystalline resin composition (such as an aromatic polyester resin composition) in which crystallization (or crystallinity) is promoted (or improved or improved) is obtained by the crystallization accelerator of the present invention. The present invention also includes such a resin composition, that is, a resin composition containing a crystalline resin (such as an aromatic polyester resin) and a crystallization accelerator.

  The resin composition may contain other resins as long as the effects of the present invention are not impaired. For example, in a resin composition containing an aromatic polyester resin as a crystalline resin, as another resin, a crystalline resin or an amorphous resin, for example, an olefin resin {for example, a chain olefin resin [for example, an ethylene-based resin (for example, polyethylene ), Propylene resin (eg, polypropylene), polymethylpentene, etc.], cyclic olefin resin, etc.}, halogen-containing vinyl resin (polyvinyl chloride, fluororesin, etc.), acrylic resin, styrene resin, polycarbonate resin (eg, , Aromatic polycarbonate resin, etc.), polythiocarbonate resin, aliphatic polyester resin (polylactic acid, etc.), polyacetal resin, polyamide resin (for example, polyamide 6, polyamide 66, polyamide 610, polyamide 11, polyamide 12, polyamide 612, Aliphatic polyamide resins such as polyamide 6/66; aromatic polyamide resins such as polyamide MXD), polyphenylene ether resins, polysulfone resins, polyphenylene sulfide resins, polyimide resins, polyether ketone resins, thermoplastic elastomers such as thermoplastic elastomers, etc. May be included. These resins may be used alone or in combination of two or more.

  The ratio of the other resin is, for example, 1 to 1000 parts by weight, preferably 3 to 500 parts by weight (for example, 4 to 300 parts by weight) with respect to 100 parts by weight of the crystalline resin (aromatic polyester resin or the like). More preferably, it may be about 5 to 100 parts by weight, and usually about 1 to 100 parts by weight (for example, 2 to 80 parts by weight, preferably 3 to 50 parts by weight).

  Further, the resin composition may contain various additives [for example, fillers or reinforcing agents, colorants (dye pigments), conductive agents, flame retardants, plasticizers, lubricants, stabilizers (antioxidants, ultraviolet rays). Absorbers, heat stabilizers, etc.), mold release agents, antistatic agents, dispersants, flow regulators, leveling agents, antifoaming agents, surface modifiers, low stress agents, carbon materials, etc.] Good. These additives may be used alone or in combination of two or more.

  The resin composition is obtained by mixing a crystalline resin (such as an aromatic polyester resin), a fluorene compound (a crystallization accelerator) and [and other components (such as additives) as necessary]. be able to. The mixing method is not particularly limited, and may be mixed by, for example, melt kneading, or may be mixed by dissolving each component in a solvent.

  The molded body formed with the resin composition is also included in the present invention. The shape of the molded body is not particularly limited and can be appropriately selected depending on the application. For example, a two-dimensional structure (film shape, sheet shape, plate shape, etc.), a three-dimensional structure (tubular, rod-shaped, tubular shape, hollow) Etc.).

  In particular, the resin composition of the present invention is often excellent in various optical properties, and an optical material or an optical molded body (particularly, an optical film, an optical lens, etc.) may be suitably formed.

  The molded body can be manufactured using, for example, an injection molding method, an injection compression molding method, an extrusion molding method, a transfer molding method, a blow molding method, a pressure molding method, a casting molding method, and the like.

  In particular, the resin composition of the present invention is often excellent in optical properties, and is useful for forming a film (particularly an optical film). Therefore, the present invention also includes a film (such as an optical film) formed from the resin composition. A film (such as an optical film) can be produced by forming (or molding) the resin composition using a conventional film forming method, casting method (solvent casting method), melt extrusion method, calendar method, or the like.

  The thickness of the film can be selected from the range of about 1 to 1000 μm depending on the application, and may be, for example, 1 to 200 μm, preferably 5 to 150 μm, and more preferably about 10 to 120 μm.

  The film may be a stretched film (uniaxially stretched film or biaxially stretched film). The stretching ratio may be about 1.05 to 10 times (for example, 1.1 to 5 times) in each direction in uniaxial stretching or biaxial stretching, and is usually 1.1 to 3 times (for example, 1. 2 to 2.5 times). In the case of biaxial stretching, it may be equal stretching or partial stretching. In the case of uniaxial stretching, longitudinal stretching or lateral stretching may be used. The stretching method is not particularly limited. In the case of uniaxial stretching, a wet stretching method or a dry stretching method may be used. In the case of biaxial stretching, a tenter method (also referred to as a flat method), a tube method, or the like may be used. Good.

  The stretched film may have a thickness of, for example, 1 to 150 μm, preferably 3 to 120 μm, and more preferably about 5 to 100 μm.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
After melting polyethylene terephthalate resin (A-PET, manufactured by Toyobo Co., Ltd.) with Laboplast mill, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene (biscresol fluorene, Osaka Gas Chemical Co., Ltd.) (Hereinafter referred to as “BCF”) at a predetermined temperature (270 ° C. when the proportion of BCF is 0% by weight and 1% by weight, and 250 ° C. when the proportion is 10% by weight and 30% by weight). ) To obtain a resin composition. In addition, the resin composition was transparent and mixed uniformly in any ratio.

  The obtained resin composition was dried at 120 ° C. and hot-pressed at 260 ° C. to produce a sheet. Furthermore, after heat-treating the obtained sheet | seat at 150 degreeC, it heat-stretched by the stretch temperature of 140 degreeC and the draw ratio of 1.2 time in the silicone oil bath, and obtained the stretched film.

  Using the obtained stretched film, a differential scanning calorimeter (manufactured by Rigaku Corporation, Thermo plus DSC 8230) was used in nitrogen, at a heating rate of 10 ° C./min. The transition temperature (Tg) was measured. In addition, regarding the heat of fusion, two types of heat of fusion of the resin composition and the resin were calculated. That is, the heat of fusion of the resin composition indicates the heat of fusion per weight of the entire resin composition, and the heat of fusion of the resin indicates the heat of fusion per weight of the resin in the resin composition.

  In addition, a sample (thickness 0.2 mm, width 5 mm, length 50 mm) was prepared from the obtained stretched film, and a chuck tester (Tensilon RTC-1250 (A & D)) was used with this sample. The strength until the sample was cut at a pulling speed of 2 mm / min was measured at a distance of 20 mm. In this tensile test, the maximum strength (maximum strength) was also measured.

  Further, for the obtained stretched film (thickness 2 mm), the refractive index and the Abbe number were measured at the temperatures (measurement temperatures) shown in Table 1 using an Abbe refractometer (manufactured by Atago).

  The results are shown in Table 1. In Table 1, for comparison, the result of the BCF ratio of 0% by weight is also shown.

  As is apparent from the results in Table 1, the addition of BCF increased the heat of fusion, which is an index of ease of crystallization, in both the polyethylene terephthalate resin and the resin composition. It was also found that Tg also increased. Furthermore, mechanical strength (tensile strength) was also improved. Furthermore, the Abbe number also increased.

(Example 2)
Example 1 was used except that 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka Gas Chemical Co., Ltd., hereinafter referred to as BPEF) was used instead of BCF. Measured in the same manner as above. The results are shown in Table 2.

  As apparent from the results in Table 2, even when BPEF was added, an increase in heat of fusion could be confirmed. Furthermore, Tg and mechanical strength (tensile strength) were also improved.

(Example 3)
In Example 1, it measured like Example 1 except having replaced with polyethylene terephthalate resin and using polyethylene naphthalate resin (Kanebo Co., Ltd. product, H-PEN). The mixing temperature was 280 ° C., the hot press temperature was 270 ° C., the heat treatment temperature was 190 ° C., and the stretching temperature was 180 ° C.

  In the measurement with a differential scanning calorimeter, the crystallization start temperature (that is, the crystallization start temperature at the time of temperature increase) (Tc) was also measured. Further, for the obtained stretched film, a birefringence (Δn / increase per unit magnification) at the time of stretching was obtained by using a polarizing microscope (manufactured by NIKON Co., Ltd., OPTIPHOT-POL) to cancel the polarization with a compensator. λ) was measured. The results are shown in Table 3.

  As is clear from the results in Table 3, an increase in the heat of fusion could also be confirmed in the polyethylene naphthalate resin. Moreover, the decrease of Tc was also confirmed. The reason why Tc could not be confirmed at 30% by weight is considered to be because the crystallinity became very high. In addition, the Abbe number also increased. Furthermore, the birefringence decreased.

Example 4
In Example 1, measurement was performed in the same manner as in Example 1 except that polyethylene naphthalate resin (manufactured by Kanebo Co., Ltd., H-PEN) was used instead of polyethylene terephthalate resin, and BPEF was used instead of BCF. did. The mixing temperature was 260 ° C., the hot press temperature was 270 ° C., the heat treatment temperature was 190 ° C., and the stretching temperature was 180 ° C.

  In the measurement with a differential scanning calorimeter, the crystallization start temperature (that is, the crystallization start temperature at the time of temperature increase) (Tc) was also measured. Further, the birefringence of the obtained stretched film was measured in the same manner as in Example 3. The results are shown in Table 4.

  As apparent from the results in Table 4, even when BPEF was added to the polyethylene naphthalate resin, an increase in heat of fusion could be confirmed. In particular, it can be seen that the heat of fusion significantly increases and the crystallinity is extremely improved. Moreover, the decrease of Tc was also confirmed. The reason why Tc could not be confirmed at 10% by weight and 30% by weight is considered to be that crystallization progressed completely during the evaluation sample formation process because the crystallization rate was very fast. In addition, the Abbe number also increased. Furthermore, the birefringence decreased.

(Example 5)
In Example 1, it measured like Example 1 except having replaced with the polyethylene terephthalate resin and having used polybutylene terephthalate resin (Toyobo Co., Ltd. product, PBT). In the measurement with a differential scanning calorimeter, the crystallization start temperature (that is, the crystallization start temperature at the time of temperature increase) (Tc) was also measured. The results are shown in Table 5.

  As is clear from the results in Table 5, an increase in heat of fusion could be confirmed even when BPEF was added to the PBT resin. In particular, it can be seen that the heat of fusion significantly increases and the crystallinity is improved. Moreover, the improvement of the crystallization temperature at the time of temperature fall was also confirmed.

  The additive of the present invention can be used as an additive for promoting or increasing the crystallization of a crystalline resin (such as an aromatic polyester resin). Moreover, such additives can also provide effects other than the promotion of crystallization, such as improved mechanical properties, improved heat resistance, reduced birefringence, improved both refractive index and Abbe number, Highly useful.

  Therefore, the crystalline resin (or resin composition) modified (accelerated crystallization) by the additive of the present invention depends on the type of resin to be combined, for example, high crystallinity, high Abbe number, and high refraction. It has excellent properties such as rate, high strength, high heat resistance, and high transparency. Such a resin composition can be suitably used particularly for an optical lens, an optical film, an optical sheet, a pickup lens, a hologram, a liquid crystal film, an organic EL film, and the like. Resin compositions include paints, antistatic agents, inks, adhesives, pressure-sensitive adhesives, resin fillers, charging trays, conductive sheets, protective films (protective films for electronic equipment, liquid crystal members, etc.), electrical / electronic materials (Carrier transport agent, luminous body, organic photoreceptor, thermal recording material, hologram recording material), electrical / electronic component or equipment (optical disk, inkjet printer, digital paper, organic semiconductor laser, dye-sensitized solar cell, EMI shield film) Resin for photochromic materials, organic EL elements, color filters, etc.), resin for mechanical parts or equipment (automobiles, aerospace materials, sensors, sliding members, etc.) and the like.

  In particular, since the resin composition is excellent in optical characteristics, it is useful for constituting (or forming) a molded product for optical use (optical molded product). Examples of the optical molded body formed (configured) with such a resin composition include an optical film and an optical lens.

  As an optical film, a polarizing film (and a polarizing element and a polarizing plate protective film constituting it), a retardation film, an alignment film (alignment film), a viewing angle expansion (compensation) film, a diffusion plate (film), a prism sheet, Light guide plate, brightness enhancement film, near infrared absorption film, reflection film, antireflection (AR) film, reflection reduction (LR) film, antiglare (AG) film, transparent conductive (ITO) film, anisotropic conductive film (ACF) ), Electromagnetic wave shielding (EMI) film, film for electrode substrate, film for color filter substrate, barrier film, color filter layer, black matrix layer, adhesive layer or release layer between optical films. In particular, the film of the present invention is useful as an optical film for use in an apparatus display. Specific examples of the display member (or display) including the optical film of the present invention include FPD devices such as personal computer monitors, televisions, mobile phones, car navigation systems, and touch panels (for example, , LCD, PDP, etc.).

Claims (14)

A crystallization accelerator composed of a compound represented by the following formula (1), which is an additive for promoting crystallization of an aromatic polyester resin.
[Wherein ring Z is an aromatic hydrocarbon ring, R ¹ and R ² are substituents, X is a group — [(OR ³ ) nY] (wherein Y is a hydroxyl group, a mercapto group, glycidyl An oxy group or a (meth) acryloyloxy group, R ³ is an alkylene group, n is an integer of 1 to 12 ) or an amino group, k is an integer of 0 to 4, m is an integer of 0 or more, p is 1 or more Indicates an integer. ] The crystallization accelerator according to claim 1, wherein the compound having a 9,9-bisarylfluorene skeleton is a compound represented by the following formula (1A).
(In the formula, Z, R ¹ , R ² , k, m, R ³ , n, and p are the same as those in the formula (1).) Ring Z is a monocyclic or condensed polycyclic aromatic hydrocarbon ring, R ¹ is an alkyl group, k is 0 or 1, R ² is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group, m is The crystallization accelerator according to claim 1 or 2, wherein 0 to 2, R ³ is a C _2-4 alkylene group, n is 1 to 4 , and p is 1 to 3. Compounds having a 9,9-bisaryl fluorene skeleton, 9, 9-bis (hydroxyalkoxy phenyl) fluorene, 9,9-bis (alkyl - hydroxyalkoxy phenyl) fluorene, 9,9-bis (aryl - hydroxy alkoxyphenyl 4. The crystallization accelerator according to any one of claims 1 to 3, which is at least one selected from fluorene and 9,9-bis (hydroxyalkoxynaphthyl) fluorene. Ring Z is a benzene ring or a naphthalene ring, R ² is a C _1-4 alkyl group or a C _6-10 aryl group, m is 0 to 2, R ³ is a C _2-3 alkylene group, n is 1 or 2, The crystallization accelerator according to any one of claims 1 to 4, wherein p is 1 or 2. The crystallization accelerator according to any one of claims 1 to 5 , wherein the aromatic polyester resin is a polyalkylene arylate resin. Furthermore, it is an additive for improving (1) mechanical strength, (2) Abbe number, and / or (3) heat resistance, The crystallization promoter in any one of Claims 1-6 . A resin composition comprising an aromatic polyester resin and the crystallization accelerator according to any one of claims 1 to 7 . The resin composition according to claim 8 , wherein the proportion of the crystallization accelerator is 0.1 to 50 parts by weight with respect to 100 parts by weight of the aromatic polyester resin. The molded object formed with the resin composition of Claim 8 or 9 . The molded article according to claim 10, which is an optical molded article. The molded article according to claim 10 or 11, which is an optical film. Molded body according to any one of claims 10 to 12, which is a stretched film. Aromatic polyester resins, a method of adding a crystallization accelerator according to any one of claims 1 to 7 to promote crystallization of the aromatic polyester resin.